协同双原子催化剂在铈上增强CO优先氧化：来自高通量第一原理微动力学的见解

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-12-24 DOI:10.1021/acscatal.4c05779

Zhang Liu, Yanwei Wen, Zhaojie Wang, Limin Guo, Rong Chen, Aimin Zhang, Bin Shan

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引用次数: 0

摘要

高度分散的过渡金属原子作为CO优先氧化（PROX）催化剂受到了广泛的关注。双原子催化剂（dac）通过协同效应有效地平衡了活性和选择性，是PROX催化的有希望的候选材料。本文报道了基于第一线微动力学原理的高通量筛选CeO2（110）负载的dac （MA- mb /CeO2， MA(B) = 3d, 4d， 5d过渡金属）。通过结合能和聚集能分析，金属原子的电负性降低和d轨道居群有利于负载dac的稳定性。对整个PROX反应网络的状态-状态微动力学分析表明，以直接氧化、碳酸盐形成和界面氧迁移为特征的O2预解Mars-van Krevelen （MvK）途径是低温下MA-MB/CeO2的主要机制。均相dac的关键能量路线表明，解离O2的除氧能和过渡金属位点上CO和H的吸附能是PROX性能的有效描述符。根据这些见解，在435种异相dac的组合上进行了PROX描述子的高通量计算，以筛选具有平衡活性和选择性的催化剂。以au为基础的dac，特别是Fe-Au，在室温下因其易于激活解离氧和缓和的氢亲和力而脱颖而出。我们的研究利用了双原子构型的独特性质，为合理设计高效的PROX催化剂铺平了道路。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Synergistic Dual-Atom Catalysts on Ceria for Enhanced CO Preferential Oxidation: Insights from High-Throughput First-Principles Microkinetics

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Synergistic Dual-Atom Catalysts on Ceria for Enhanced CO Preferential Oxidation: Insights from High-Throughput First-Principles Microkinetics

Highly dispersed transition metal atoms supported by reducible ceria have garnered considerable attention as CO preferential oxidation (PROX) catalysts. Dual-atom catalysts (DACs), which effectively balance activity and selectivity through synergistic effects, are promising candidates for PROX catalysis. We report here the high-throughput screening of CeO₂(110)-supported DACs (M_A-M_B/CeO₂, M_A(B) = 3d, 4d, 5d transition metal) based on first-principles microkinetics. Reduced electronegativity and d-orbital population of metal atoms favor the stability of loaded DACs via binding energy and aggregation energy analyses. A state-to-state microkinetic analysis of the full PROX reaction network identifies that the O₂ -predissociated Mars–van Krevelen (MvK) pathway, characterized by direct oxidation, carbonate formation, and interfacial oxygen migration, is the predominant mechanism on M_A-M_B/CeO₂ under low temperatures. The key energetic routes of homogeneous DACs reveal that the oxygen removal energy of dissociated O₂ and adsorption energies of CO and H on transition metal sites serve as effective descriptors of PROX performance. Following these insights, high-throughput computations of PROX descriptors are carried out on a combination of 435 heterogeneous DACs to screen catalysts with balanced activity and selectivity. Au-based DACs, notably Fe–Au, stand out at room temperature for their facile activation of dissociated oxygen and moderated hydrogen affinity. Our study harnesses the unique properties of dual-atom configurations and paves way for the rational design of efficient PROX catalysts.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.